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51.
J. C. Kennedy P. Nadeau Z. J. Petryka R. H. Porrier G. Weagle 《Photochemistry and photobiology》1992,55(5):729-734
The clearance times of 17 different porphyrin derivatives from SKH:HR-1 mice have been measured using the technique of in vivo fluorescence spectroscopy. This technique monitors the in vivo porphyrin fluorescence observed from the external skin surface. Most hydrophilic porphyrin derivatives show relatively short clearance times, in the order of 2.5-6 h. The dicarboxylic acid porphyrins, proto-, hydroxyethylvinyldeutero- and hematoporphyrin IX have clearance times of 7.8, 12.2 and 14.7 h respectively. The mixture hematoporphyrin derivative has an intermediate clearance time of 12.6 h. N-methylated porphyrins show clearance times in the vicinity of 15-22 h. Monoaspartyl chlorin e6 shows the longest clearance time of all porphyrin derivatives measured (30.3 h). 相似文献
52.
Broja M. Mandal Joseph P. Kennedy Rodney Kiesel 《Journal of polymer science. Part A, Polymer chemistry》1978,16(4):821-831
An improved synthesis of trivinylaluminum (V3Al) is described. The proton magnetic resonance (PMR) spectrum of V3Al was recorded and analyzed. A new vinylation method involving the use of V3Al as the vinylating agent has been developed, and the vinylation of organic halides by V3Al was studied at ?30, ?50 and ?70°C. Primary alkyl chlorides, such as methyl and methylene chloride, do not react with V3Al and were used as solvents. Secondary chlorides such as 2-chloropropane also do not react. t-Butyl chloride gives rise to t-butylethylene (70–98%), depending on reaction conditions, and the allylic chlorides, 3-chloro-1-butene, and 3-chloro-3-methyl-1-butene, yield the expected vinylated products and their isomers (~90%). Allyl and benzyl chloride do not react under the conditions tried. The reaction between V3Al and the ditertiary dichloride 2,6-dichloro-2,6-dimethylheptane yields several isomeric C13H24 and C11H20 hydrocarbons; however, surprisingly, C9H16 does not form. The C13 hydrocarbons arise by divinylation at the termini of the dichloride, while the C11 hydrocarbons are formed by vinylation at one and proton elimination at the other terminus of the dichloride. The presence of unsaturated C13H24 and C11H20 isomers is most likely due to proton induced isomerization. These results are explained by a proximity effect involving vinylation at one end of the dichloride by V3Al followed by rapid reaction of the second chlorine (mostly) by V2AlCl generated in situ during the first vinylation in the proximity of the chloride. At the other chlorine terminus V2AlCl causes either a second vinylation (leading to C13 hydrocarbons) or a proton elimination (leading to C11 hydrocarbons). The absence of C9H16 among the reaction products indicates that V3Al exclusively effects vinylation. The RCl + V3Al ← RV + V2AlCl reaction may be regarded as a model for initiation followed by immediate termination in cationic olefin polymerization, a process leading to vinyl-ended polymers. 相似文献
53.
An INAA technique employing beta spectrometry was developed for the determination of phosphorus in polymers. The (n,γ) reaction
on phosphorus produces32P, half-life 14.3 days, a pure beta emitter with end-point energy 1.71 MeV. Polymer samples in the form of powders, films
and pellets are irradiated and then counted with a plastic scintillator. The beta spectrum is corrected for interferences
(especially Sb, Zn and Br which are quantified by gamma spectrometry) and for energy loss in the thick sample. Samples must
also be analyzed for S and Cl which cause nuclear interferences. With an irradiation time of 4 hours at a neutron flux of
5·1011 n·cm−2
s
−1, decay time 10 days and counting time 10 minutes, the sensitivity is 520 counts/μg phosphorus and the detection limit is
typically 2μg/g. 相似文献
54.
55.
This series of papers concern new materials for possible biological applications created by combining the chemistry of highly reactive cyanoacrylates (CAs) with polyisobutylene (PIB) rubbers. First, a new strategy for the synthesis of CA–telechelic PIBs is described. Subsequently, the strategy is employed for the synthesis of low viscosity (syringible) CA–telechelic three‐arm star PIB [Ø(PIB–CA)3]. The intermediates of the synthesis route are characterized by 1H NMR spectroscopy. Injecting liquid Ø(PIB–CA)3 into living tissue (fresh chicken egg) produces a bolus of crosslinked PIB rubber. The spectacular oxidative resistance of this rubber is documented by its resistance to concentrated HNO3. A structural model of the crosslinked rubber obtained upon contacting Ø(PIB–CA)3 with proteinaceous tissue is proposed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
56.
Zhengjie Pi Joseph P. Kennedy James W. Summers 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3644-3651
The tertiary chlorine (Clt) content of vinyl chloride/2‐chloropropene copolymers [P(VC‐co‐2CP)] was determined by NMR spectroscopy. Copolymers containing 6.8–47.0 Clt's per P(VC‐co‐2CP) chain were used to initiate the cationic grafting of α‐methylstyrene, norbornadiene, indene, and norbornene with Et2AlCl under various conditions. Grafting was demonstrated by selective solvent extraction, and the effect of the experimental conditions on the grafting efficiency was examined. Select rheological and thermal characteristics of P(VC‐co‐2CP) grafts, including the glass‐transition temperature, heat deflection temperature, and discoloration upon heating, were studied. P(VC‐co‐2CP) carrying 7–11 poly(α‐methylstyrene) or polynorbornadiene branches per chain raised the glass‐transition temperature to, or above, that of a blend control. P(VC‐co‐2CP)s fitted with polyindene or polynorbornene branches were less effective in raising the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3644–3651, 2002 相似文献
57.
Bodwell GJ Bridson JN Cyrañski MK Kennedy JW Krygowski TM Mannion MR Miller DO 《The Journal of organic chemistry》2003,68(6):2089-2098
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